Synthesis, Crystal Structures and Characterization of Nickel(II) Complexes with Dithiobenzoate Derivatives
Synthesis, Crystal Structures and Characterization of Nickel(II) Complexes with Dithiobenzoate Derivatives
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DOI：
10.1016/j.rechem.2022.100470
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发表时间：
2022-08
影响因子：
2.3
通讯作者：
T. Nishiyama;Naohiro Takahashi;Takuto Mibu;M. Maekawa;T. Kuroda–Sowa;Y. Suenaga;T. Okubo
中科院分区：
文献类型：
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作者：
T. Nishiyama;Naohiro Takahashi;Takuto Mibu;M. Maekawa;T. Kuroda–Sowa;Y. Suenaga;T. Okubo
合成了新的二硫代苯甲酸镍配合物[NiII(Me-DTB)2]和[NiII(Oct-DTB)2]2(Me-DTB=4-甲基二硫代苯甲酸酯和OCT-DTB=4-辛基-二硫代苯甲酸酯)，并用X-射线衍射法对其结构进行了表征。[NiII(Me-dtb)2]具有单核结构，包括具有正方形平面配位几何构型的镍(II)离子，[NiII(Oct-dtb)2]2在镍离子的顶端位置通过弱的Ni···S相互作用连接而成双核结构。这些络合物的溶液在约600 nm处表现出较强的光吸收，呈深蓝色。为了揭示Ni(II)-二硫代苯甲酸酯配合物的电子状态和光吸收机理，分别用DFT/B3LYP方法和TD-DFT/CAM-B3LYP方法对[NiII(Dtb)2](dtb=二硫代苯甲酸)和[NiII(Me2dtc)2](Me2dtc=二硫代氨基甲酸酯)进行了基态分子结构优化和激发态计算。
New nickel(II) complexes with dithiobenzoate ligands, [NiII(Me-dtb)2] and [NiII(Oct-dtb)2]2(Me-dtb = 4-methyl-dithiobenzoate and Oct-dtb = 4-octyl-dithiobenzoate), were synthesized and structurally characterized using X–ray diffraction analysis. [NiII(Me-dtb)2] has a mononuclear structure, including a nickel(II) ion with a square planar coordination geometry, and [NiII(Oct-dtb)2]2has a dinuclear structure connected by weak Ni•••S interactions in the apical position of the nickel ion. The solutions of these complexes show strong light absorption at approximately 600 nm with a dark blue color. To reveal the electronic states and mechanism of the light absorption of Ni(II)- dithiobenzoate complexes, optimization of the ground-state molecular structures and excited-state calculations for [NiII(dtb)2] (dtb = dithiobenzoate) and [NiII(Me2dtc)2] (Me2dtc = dimethyl-dithiocarbamate) were performed by DFT/B3LYP method and TD-DFT/CAM-B3LYP method, respectively.